Treatment of hydrocarbon oils



Aug. 14, 1934.

J. c. MORRELL TREATMENT 0F HYDROCARBON OILS Filed Feb. 14, 1930 IIIII INVENToR JacgueCMor Il BY ATTORNEY Patented Aug. 14, 1934 issasis TREATMENT or maocannos olLs Jacque c. Morrell, emma, m., mignon a Universal Oil Products Company, Chicago, Ill.,

a corporation of South Dakota Application February 14, 1930, Serial No. 428,489 3 Claims. (Cl. 196-62) This invention relates to a process for the treatment of hydrocarbon oils, and refers more particularly to a process for the hydrogenation of oils at elevated temperatures.

5 Among the objects of the process is to increase the yield of the lower boiling products madeby the thermal decomposition or cracking of higher boiling oils; to` saturate in part the more highly unsaturated hydrocarbons, especially those which 1.0 form gums, polymers, and other undesirable materials in the motor fuel product; and to desulfurize` in part the hydrocarbons to render them more suitable for motor fuel and to facilitate and reduce the cost of refining.

l5 It is not the purpose' of this invention necessarily to completely saturate the hydrocarbons of the olefin series to produce paramn hydrocarbons, but rather to add hydrogen in regulated amounts to the more highly unsaturated hydrocarbons for the aforementioned purposes.

In the present invention, the hydrocarbons are treated in the vapor state. Gasoline, which is the major product of the cracking process, contains highly unsaturated hydrocarbons which upon standing polymerize and oxidize to form gums, tars,` and other undesirable substances. The presence of sulfur compounds in a motor fuel may result in destructive corrosion of the crankcase and other parts of the motor during combustion and may also result in the destructive corrosion of the cracking or distillation equipment.

Among the Afurther objects of my invention is the minimizing ofI these objectionable features.

In the specific embodiment of my invention, hydrocarbon oils in the vapor state and basic materials or alkali, or substances giving an alkaline reaction are mixed with finely divided metals which react with the alkali at elevated temperatures to produce hydrogen. Preferably, the alkali 40 is introduced into the oil in aqueous solution.

As examples of alkalies, the hydroxides of sodium, potassium, ammonium, calcium, barium, v strontium, and/or the corresponding oxides and carbonates may be used.

In the operation of the process of my invention, finely divided metals and basic or alkaline materials are introduced simultaneously in those portions of the cracking system where the oil is in the vapor state, c g., in the reaction chamber and 50 dephlegmator and connecting lines or vapor line to the condenser or enlarged portion thereof. The

steam reacts with the finely divided metal forming hydrogen in situ. The newly liberated hydrogen, which is more active than ordinary molecular hydrogen and is sometimes spoken of as being in v the nascent state, reacts with the chemically unsaturated portions of the oil vapors as well as with sulfur compounds, saturating in part the oleflnic hydrocarbons and reducing some of the higher sulfur compounds to hydrogen sulde 60 which may readily be removed from the final products.

As examples of metals, I may use sodium, potassium, calcium, magnesium, zinc, aluminum. iron, tin, and others, including alloys and amal- 05 gam preferably the metals which are electro-` negative to hydrogen, i.e., whichare above hydrogen in the electromotive series, and which liberate hydrogen from steam. lT'he corresponding oxides of the metals formed by the reaction with .70 the alkalies have some catalytic action in promoting the hydrogenation and desulfurization reaction 'as well as assisting in the cracking reaction. The use of nely divided metals has an additional advantage in that the ner the metal the greater the surface exposure and consequently the great- 'er the velocity or rate of reaction.

In addition to the above I may also add molecular hydrogen to the materials undergoing reaction in order to assist in the reaction, or I may add gases containing hydrogen such as gases from oil cracking, coke oven gas, producer gas, natural gas,l etcetera.

In operating the process of the invention I may .make use of any conventional apparatus or equipment suitable for cracking, but preferably I make use of a cracking system consisting of heating tubes` or elongated pipe or heating coil in combination with a reaction chamber, dephlegmator or fractionating means and the auxiliary cooling, condensing, and collecting devices. In the operation of the process I preferably return the reux condensate or distillates condensed in the dephlegmating or fractionating means to the heating element for reconversion.

Preferably the oil is heated to a cracking temperature, although my invention contemplates operating the process at lower temperatures also. Preferably the process is operated at superatmospheric pressure, and may in some cases also be 10 operated at atmospheric'or reduced or subatmospheric pressures. Generally I make use of superatmospheric pressures ranging from 'l5 pounds to 3000 pounds, more or less, and at temperatures of from approximately 400 to 1400" F.

As an example of the results obtained by the process, a 27 degree Baum gravity Mid-Continent topped crude when subjected to a cracking temperature of approximately 920 F. and a pressure of approximately 1000 pounds per square '110 inch using approximately of a mixture of ilnely divided aluminum and iron and about 10% by volume of a saturated solution of caustic soda based on the reilux condensate recycled through the heating tubes shows an approximate yield of gasoline of sixty percent.. in addition to approximately of pressure-distillate bottoms or gas oil which may be utilized as recycle stock. Coke and gas are also' valuable products of the process. The sulfur contmt of the gasoline produced, which would normalLy be approximately 0.3 percent., may be reduced to approximately 0.1 percent.

The above example is illustrative and is not intended tobe fully descriptive of the broad possibilities of the process, and hence should not be construed as a. limitation upon the invention.

The accompanying drawing is a diagrammatic illustration of the process. y

I claim as my invention: y

1. In the art of cracking heavy hydrocarbon oil for the production of gasoline and wherein the oil is heated to cracking temperature under pressure while flowing in arestricted stream thru a/heating zone, thence discharged into a reaction zone maintained under cracking conditions, and the cracked vapors fractionated in a dephlegmating zone to condense and separate -ing with each other to form hydrogen whereby the highly unsaturated gum-forming hydrocarbons of the cracked gasoline vapors are saturated prior to final condensation of the gasoline vapors.

moeders 2. In the art of cracking heavy hydrocarbon oil for the production of gasoline and wherein the oil is heated to cracking temperature under pressure while ilowing in a restricted stream thru a heating zone, thence discharged into areaction zone maintained under cracking conditions, and the cracked vapors fractionated in a dephlegmating zone to condense andseparate insuiciently cracked fractions thereof; the improvement which comprises introducing into the vapors undergoing treatment in said reaction zone finely divided metal and aqueous alkaline solution capable of reacting with each other to form hydrogen whereby the highly unsaturated gumforming hydrocarbons of the cracked gasoline vapors are saturated prior to hnal condensation of the gasoline vapors.

3. In the art of crackingsheavy hydrocarbonv oil for the production of gasolixe and wherein the pil is heated to cracking temperature under pressure while flowing in a restricted stream thru Jacqui: c. MoRRmL.

lisy 

